CN106883501A - A kind of enhanced ecological degradative plastic film in Techniques in Dry-farming Areas and preparation method thereof - Google Patents
A kind of enhanced ecological degradative plastic film in Techniques in Dry-farming Areas and preparation method thereof Download PDFInfo
- Publication number
- CN106883501A CN106883501A CN201710166070.8A CN201710166070A CN106883501A CN 106883501 A CN106883501 A CN 106883501A CN 201710166070 A CN201710166070 A CN 201710166070A CN 106883501 A CN106883501 A CN 106883501A
- Authority
- CN
- China
- Prior art keywords
- tunic
- weight
- weight portion
- stearate
- wholly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
- A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
- A01G13/0256—Ground coverings
- A01G13/0262—Mulches, i.e. covering material not-pre-formed in mats or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0017—Combinations of extrusion moulding with other shaping operations combined with blow-moulding or thermoforming
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
Abstract
A kind of degradation time the present invention relates to Dryland biodegradable material, including the first tunic and the second tunic, and the first tunic is more than the degradation time of the second tunic；The raw material components of the first tunic include degradation agent, heat stabilizer, light stabilizer, antioxidant, low density polyethylene (LDPE) and LLDPE；The raw material components of the second tunic include starch, silica, silane coupler, polyvinyl alcohol, degradation agent, low density polyethylene (LDPE) and LLDPE.The Dryland biodegradable material that the present invention is provided, fully combine the advantage of polythene material and starch, using double-decker, not only there is excellent mechanical performance and water resistance, and be easy to degraded, it is in actual use, each several part can simultaneously reach degraded terminal, so as to eliminate the conventional commercial degradative plastic film defect that each several part degradation rate differs in application process, and then winding of the residual film to machinery is greatly reduced, significantly promote the development of agricultural productive force.
Description
Technical field
The present invention relates to ground technical field of membrane, and in particular to a kind of enhanced ecological degradative plastic film in Techniques in Dry-farming Areas and its system
Preparation Method.
Background technology
The heating, preserve soil moisture of agricultural mulching covering, the function such as frost protection, are greatly promoted carrying for farm output and benefit
Height, has driven the transformation of mode of agriculture and the leap aspect of agricultural productive force.According to statistics, the popularization of film-mulching technique should
With, make whole world crops fit kind of area Northern Hemisphere and Southern Hemisphere is to the south respectively, north elapsed 2 ° -4 ° of geographic latitude, to mountain region high
Area has elapsed 500-1000m height above sea levels, and crop generally increases production 30%-50%, and rise in value 40%-60%.Plastic film it is a large amount of
Use " White Revolution " that brings in agricultural production.The mulch film application being prepared from using artificial synthesized macromolecule PE materials is most
For extensive, but it is difficult degraded under field conditions (factors)；And mulch film application is over more than 30 years, due to people's environmental consciousness it is delayed with
And the effective shortage of used plastic collection measure, the agricultural land soil of the current long-term overlay film of China, average every mu of mulch film residual quantity is up to 5-
15 kilograms.The mulch film fragment of a large amount of residuals is difficult by soil microbial degradation, and longer-term persistence causes soil texture to break in farmland
Bad, farmland quality degradation；Additionally, the presence of a large amount of residual films causes farming to operate be obstructed, to next season crops agrarian zone
To adversely affect, the development of agricultural aspect productivity is seriously hindered.It is dirty that the appearing as of Biodegradable mulch solves agricultural mulching
Dye provides an effective way.
Starch as nature enrich renewable resource, wide material sources, it is cheap, nontoxic and can completely biology
Degraded, its product has excellent environmental-protecting performance in use, can be degraded rapidly after discarding, so as to come from nature and return certainly
So.But poor mechanical property limits its application with water resistance, and substantial amounts of hydrogen is there is with intermolecular in starch molecule
Key, thus thermoplasticity is poor, it is difficult to machine-shaping, it is low to there is low mechanical strength, poor water resistance and wet strength in the product for preparing
The shortcomings of.
In recent years, although people are to starch application is studied in degradation material, but above mentioned problem is not yet
Effectively solved.Based on this, a kind of new degradable mulch of research and development is particularly important, and it will be substantially reduced farming
Production cost, and then promote agricultural productive force development.
The content of the invention
For defect of the prior art, the invention provides a kind of enhanced ecological degradative plastic film in Techniques in Dry-farming Areas and its
Preparation method.The Dryland biodegradable material that the present invention is provided, fully combines the advantage of polythene material and starch, its
Using double-decker, not only with excellent mechanical performance and water resistance, and it is easy to degraded, it is in actually used process
In, each several part can simultaneously reach degraded terminal, so as to eliminate conventional commercial degradative plastic film each several part drop in application process
The defect that solution speed differs.Additionally, the mulch film that the present invention is provided can simultaneously reach degraded terminal in actual use, from
And winding of the residual film to machinery is greatly reduced, and reduce influence of the residual film to next season crop and save human cost, enter
And significantly promote the development of agricultural productive force.
Therefore, the present invention provides following technical scheme：
In a first aspect, a kind of Wholly-degradable material, Wholly-degradable material uses double membrane structure, including the first tunic and the second layer
Film, and the first tunic degradation time more than the second tunic degradation time；Wherein, the raw material components of the first tunic are by weight
Meter, including：Degradation agent 0.01-0.10 weight portions, heat stabilizer 0.20-0.40 weight portions, light stabilizer 0.10-0.30 weight
Part, antioxidant 0.05-0.20 weight portions, LLDPE 5-10 weight portions and LLDPE 89-94.64
Weight portion；The raw material components of the second tunic by weight, including：Starch 15-45 weight portions, nano silicon 1-5 weight
Part, silane coupler 2-5 weight portions, polyvinyl alcohol 10-30 weight portions, degradation agent 0.01-0.10 weight portions, linea low density gather
Ethene 3-5 weight portions and LLDPE 9.9-68.99 weight portions.
Specifically, the Wholly-degradable material that the present invention is provided is duplicature Dryland biodegradable material, and it is as ground
During film, in actual use, the first tunic is mulch film top layer film, i.e., with the layer of air contact, the second tunic is ground film bottom
Film, i.e., the layer for being contacted with soil.The degradation time of the first tunic, more than the degradation time of the second tunic, refers to be surveyed in degradation property
In examination, such as in photooxidative degradation experiment, thermal oxidative degradation experiment or other degradation experiments, when reaching same degraded situation, first
Degradation time of the degradation time of tunic more than the second tunic.Low density polyethylene (LDPE) is commonly called as polyethylene from high pressure process, i.e., in 100-
Under the high pressure of 300MPa, peroxide catalyzed radical polymerization generation, its density is about 0.910-0.925g/cm3, fusing point is about
130 DEG C -145 DEG C, have the advantages that density is low and material is soft.Linear low density polyethylene (LLDPE) refers to ethene and a small amount of senior-alkene
The copolymer being polymerized in the presence of a catalyst, density is about 0.918~0.935g/cm3, with softening temperature higher and
Melt temperature, and have the advantages that big intensity, good toughness, extension ability are high.
In further embodiment of the invention, degradation agent includes titanium dioxide, di-iron trioxide, manganese dioxide, two
Luxuriant iron, ferric stearate, manganese stearate, cobaltous octadecanate, copper stearate, cerium stearate, Lanthanum Stearate, Praseodymium Stearate, dimethyl two
One or more in thiocarbamic acid iron and diethyldithiocar bamic acid cerium；Heat stabilizer includes barium stearate, hard
In resin acid calcium, zinc stearate, strontium stearate, magnesium stearate, barium laurate, calcium laurate, zinc laurate and Magnesium dilaurate one
Plant or various；Light stabilizer includes phenyl salicylate, 4,4- isopropylidenes double (phenol salicylate), salicylic acids to tert-butyl benzene
In ester, resorcinol monobenzoate, ESCALOL 567 and UV-531
One or more；Antioxidant includes BHT, 2,4,6- tri-butyl-phenols, 4- methylol -2, the uncles of 6- bis-
Butylphenol, butylhydroxy anisole, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and 2,
One or more in 2 '-methylene-bis(4-ethyl-6-t-butyl phenol)；Starch includes cornstarch, farina, soil
One or more in beans starch, rice starch, pea starch, sorghum starch and tapioca；Silane coupler includes 3- ammonia
Propyl-triethoxysilicane, 3- aminopropyl trimethoxysilanes, 3- glycidyl ether oxygen propyl trimethoxy silicanes, 3- methyl-props
One or more in alkene acryloxypropylethoxysilane trimethoxy silane.
In further embodiment of the invention, the melt index of low density polyethylene (LDPE) is 0.5-5.0g/10min, line
Property low density polyethylene (LDPE) melt index be 1.5-2.5g/10min, the degree of polymerization of polyvinyl alcohol is 500-1800, and alcoholysis degree is
78%-99%.
In further embodiment of the invention, low density polyethylene (LDPE) selects LD662,2012TN26,2426H, 2436H
With one or more in LD600；LLDPE is from 7042,7042T, 9020,7042N, 7042K, 218W,
One or more in 0218D, 9042 and FV149M；Polyvinyl alcohol selects in 1799,1788,1778,0588 and 0578
Plant or various.
In further embodiment of the invention, the thickness of the first tunic is 2-4 μm, and the thickness of the second tunic is 4-8 μ
m。
In further embodiment of the invention, the raw material components of the first tunic by weight, including：Praseodymium Stearate
0.03 weight portion, the weight portion of ferrocene 0.05, the weight portion of zinc laurate 0.30, the weight portion of resorcinol monobenzoate 0.20,
The weight portion of 2,4,6- tri-butyl-phenol 0.10, the weight portion of low density polyethylene (LDPE) 8 and the weight portion of LLDPE 93；The
The raw material components of two tunics by weight, including：The weight portion of cornstarch 15, the weight portion of farina 15, nano-silica
SiClx 1-5 weight portions, the weight portion of 3- aminopropyl trimethoxysilanes 5, the weight portion of polyvinyl alcohol 20, the weight of Praseodymium Stearate 0.03
Part, the weight portion of ferrocene 0.05, the weight portion of low density polyethylene (LDPE) 5 and the weight portion of LLDPE 66；Wherein, first
The thickness of tunic is 3 μm, and the thickness of the second tunic is 4 μm；The degree of polymerization of polyvinyl alcohol is 1700, and alcoholysis degree is 99%, low close
Degree polyethylene selects 9020 and FV149M of the weight portions such as 2012TN26, LLDPE selection.
Second aspect, the present invention provides a kind of preparation method of Wholly-degradable material, comprises the following steps：S101：By first
Ball-milling treatment is carried out after each raw material components mixing of tunic, is granulated afterwards, obtain ground floor membrane degradation plastic grain；S102：Will
Each raw material components in second tunic are granulated after being well mixed, and obtain second layer membrane degradation plastic grain；Wherein, by starch, silicon
The mixture and water of alkane coupling agent, degradation agent and polyvinyl alcohol are according to 1：The mass ratio of (3-5) is mixed and stirred for uniformly, adjusting pH
It is 5.8-6.3 to be worth；It is subsequently adding nano silicon to continue to stir, regulation pH value is 3.5-4.0；It is 3.5-4.0's by pH value
Product is dried, and ball-milling treatment is carried out after mixing with low density polyethylene (LDPE) and LLDPE afterwards, then by ball milling
Product granulation after reason；S103：Ground floor membrane degradation plastic grain and second layer membrane degradation plastic grain are carried out into coextrusion blow.
In further embodiment of the invention, in S101 and S102, the condition of ball-milling treatment is：Rotating speed is 350-
500rpm, the time is 200min-300min；In S101 and S102, granulation is carried out in dual-screw pelletizer, and twin-screw is made
The condition of grain machine is specially：Temperature is 170 DEG C -185 DEG C, and screw speed is 130rpm-180rpm, and screw slenderness ratio L/D is 30-
50。
In further embodiment of the invention, in S102, the condition of stirring is specially：Temperature is 40 DEG C -50 DEG C, is turned
Speed is 150rpm-250rpm, and the time is 30min-50min；In S103, coextrusion blow is carried out in double-layer coextrusion inflation film manufacturing machine, and
The condition of double-layer coextrusion inflation film manufacturing machine is specially：Temperature is 155 DEG C -160 DEG C, and blow-up ratio is 3.1-3.3, and hauling speed is 8m/
min-10m/min.Applicant has found by many experiments：Temperature is 155 DEG C -160 DEG C during blowing, and must keeping temperature perseverance
It is fixed, if temperature is higher than 160 DEG C, film embrittlement can be made, especially it is remarkably decreased longitudinal tensile strength；If temperature is less than
155 DEG C, the film of Ze Huishi production departments warm can not sleekly carry out expansion stretching, and the tensile strength of film is relatively low.Additionally, work as blowing
When swollen ratio is more than 3.3, easily there is fold in film.
The third aspect, the Wholly-degradable material that the present invention is provided answering in film product or film product additive is prepared
With, and the especially application in mulch film, hyaline membrane and packaging material product or product additive is prepared.
The above-mentioned technical proposal that the present invention is provided has advantages below：
(1) applicant has found by many experiments：The Dryland biodegradable material that the present invention is provided, fully combines
The advantage of polythene material and starch, it uses double-decker, is not only stretched with excellent water resistance and tensile strength, fracture
The mechanical performances such as rate long, and be easy to degraded, its in actual use, each several part can simultaneously reach degraded terminal, from
And eliminate the conventional commercial degradative plastic film defect that each several part degradation rate differs in application process.
(2) mulch film that the biodegradable material that the present invention is provided is prepared uses double membrane structure, and each layer is by difference
The material of degradation characteristic is made and the degradation rate of each layer is different, finally makes the mulch film for preparing in actual use,
Each several part can simultaneously reach degraded terminal, so as to eliminate conventional commercial degradative plastic film each several part degraded speed in application process
The different defect of rate, and then significantly improve the practicality of degradative plastic film.Conventional commercial degradative plastic film is in actual use
The degradation rate of each several part differs, and main forms are：Mulch film is exposed to the part (referred to as " expose portion ") and ground of air
It is huge that film is embedded in soil part (" burying native part ") degradation rate difference；Under normal circumstances, the mulch film of expose portion has reached drop
Solution terminal, mulch film becomes fragile, or even has been degraded to carbon dioxide and water；And the mulch film for burying native part is not changed in substantially, still tie up
Its initial mechanical mechanical property is held, so as to carry out detrimental effect to next season crops agrarian zone, and degradative plastic film is not reaching to
Due effect.
(3) mulch film that the biodegradable material provided using the present invention is prepared, it is each in actual application
Partial digestion is uniform and thorough, so as to the secondary pollution that the use for eliminating traditional mulch film brings to soil；And so as to without after
Continuous recovery process, eliminates winding of the residual film to subsequent mechanical, reduces influence of the residual film to next season crop and saves
Human cost, and then significantly promote the development of agricultural aspect productivity.
Specific embodiment
The embodiment of technical solution of the present invention will be described in detail below.Following examples are only used for clearer
Explanation technical scheme, therefore be only used as example, and can not be limited the scope of the invention with this.
Experimental technique in following embodiments, unless otherwise specified, is conventional method.
Test material used in following embodiments, unless otherwise specified, is what is be commercially available from conventional reagent shop.
Quantitative test in following examples, is respectively provided with three repetitions and tests, and data are three average values of repetition experiment
Or mean+SD.
The biodegradable material that the present invention is provided uses double membrane structure, including the first tunic and the second tunic, and the
Degradation time of the degradation time of one tunic more than the second tunic；Wherein, the raw material components of the first tunic by weight, are wrapped
Include：Degradation agent 0.01-0.10 weight portions, heat stabilizer 0.20-0.40 weight portions, light stabilizer 0.10-0.30 weight portions, antioxygen
Agent 0.05-0.20 weight portions, low density polyethylene (LDPE) 5-10 weight portions and LLDPE 89-94.64 weight portions；Second
The raw material components of tunic by weight, including：It is starch 15-45 weight portions, nano silicon 1-5 weight portions, silane coupled
Agent 2-5 weight portions, polyvinyl alcohol 10-30 weight portions, degradation agent 0.01-0.10 weight portions, low density polyethylene (LDPE) 3-5 weight portions with
And LLDPE 9.9-68.99 weight portions.Wherein, the thickness of the first tunic is 2-4 μm, and the thickness of the second tunic is
4-8μm。
Preferably, degradation agent includes titanium dioxide, di-iron trioxide, manganese dioxide, ferrocene, ferric stearate, stearic acid
Manganese, cobaltous octadecanate, copper stearate, cerium stearate, Lanthanum Stearate, Praseodymium Stearate, ferric dimethyl dithiocarbamate and diethyl
One or more in base aminodithioformic acid cerium；Heat stabilizer includes barium stearate, calcium stearate, zinc stearate, tristearin
One or more in sour strontium, magnesium stearate, barium laurate, calcium laurate, zinc laurate and Magnesium dilaurate；Light stabilizer includes
Phenyl salicylate, 4,4- isopropylidenes double (phenol salicylate), p-t-butylphenyl salicylate, resorcinol list benzoic acid
One or more in ester, ESCALOL 567 and UV-531；Antioxidant packages
Include BHT, 2,4,6- tri-butyl-phenols, 4- methylol -2,6- DI-tert-butylphenol compounds, tert-butyl hydroxy
Anisole, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and 2,2 '-di-2-ethylhexylphosphine oxide (4- ethyls -6-
Tert-butyl phenol) in one or more；Starch includes cornstarch, farina, potato starch, rice starch, pea
One or more in starch, sorghum starch and tapioca；Silane coupler includes 3- aminopropyl triethoxysilanes, 3- ammonia
Propyl trimethoxy silicane, 3- glycidyl ether oxygen propyl trimethoxy silicanes, 3- methacryloxypropyl trimethoxies
One or more in silane.
Preferably, the melt index of low density polyethylene (LDPE) is 0.5-5.0g/10min, the melting of LLDPE
Index is 1.5-2.5g/10min, and the degree of polymerization of polyvinyl alcohol is 500-1800, and alcoholysis degree is 78%-99%.Wherein, low-density
Polyethylene is from one or more in LD662,2012TN26,2426H, 2436H and LD600；LLDPE is selected
With one or more in 7042,7042T, 9020,7042N, 7042K, 218W, 0218D, 9042 and FV149M；Polyvinyl alcohol
From one or more in 1799,1788,1778,0588 and 0578.
Preferably, the raw material components of the first tunic by weight, including：The weight portion of Praseodymium Stearate 0.03, ferrocene
0.05 weight portion, the weight portion of zinc laurate 0.30, the weight portion of resorcinol monobenzoate 0.20,2,4,6- tri-butyl-phenols
0.10 weight portion, the weight portion of low density polyethylene (LDPE) 8 and the weight portion of LLDPE 93；The raw material components of the second tunic are pressed
Weight portion meter, including：The weight portion of cornstarch 15, the weight portion of farina 15, nano silicon 1-5 weight portions, 3- ammonia
The weight portion of propyl trimethoxy silicane 5, the weight portion of polyvinyl alcohol 20, the weight portion of Praseodymium Stearate 0.03, the weight portion of ferrocene 0.05,
The weight portion of low density polyethylene (LDPE) 5 and the weight portion of LLDPE 66；Wherein, the thickness of the first tunic is 3 μm, second
The thickness of tunic is 4 μm；The degree of polymerization of polyvinyl alcohol is 1700, and alcoholysis degree is 99%, and low density polyethylene (LDPE) selects 2012TN26,
9020 and FV149M of the weight portions such as LLDPE selection.
In addition, being directed to Wholly-degradable material of the invention, the present invention specially devises the method for preparing Wholly-degradable material, including
Following steps：
S101：Ball-milling treatment is carried out after each raw material components of the first tunic are mixed, is granulated afterwards, obtain the first tunic drop
Solution plastic grain.
S102：Granulated after each raw material components in second tunic are well mixed, obtain second layer membrane degradation plastic grain；
Wherein, by the mixture and water of starch, silane coupler, degradation agent and polyvinyl alcohol according to 1：The mass ratio mixing of (3-5) is simultaneously
Stir, regulation pH value is 5.8-6.3；It is subsequently adding nano silicon to continue to stir, regulation pH value is 3.5-4.0；Will
PH value is dried for the product of 3.5-4.0, is carried out at ball milling after mixing with low density polyethylene (LDPE) and LLDPE afterwards
Reason, then granulates the product after ball-milling treatment.Wherein, in S102, the condition of stirring is specially：Temperature is 40 DEG C -50 DEG C, is turned
Speed is 150rpm-250rpm, and the time is 30min-50min.
S103：Ground floor membrane degradation plastic grain and second layer membrane degradation plastic grain are carried out into coextrusion blow.Wherein, altogether
Squeezing to be blow molded in double-layer coextrusion inflation film manufacturing machine is carried out, and the condition of double-layer coextrusion inflation film manufacturing machine is specially：Temperature is 155 DEG C -160 DEG C,
Blow-up ratio is 3.1-3.3, and hauling speed is 8m/min-10m/min.
Preferably, ball-milling treatment is specially：Rotating speed is 350-500rpm, and the time is 200min-300min；Granulation is in double spiral shells
Carried out in bar comminutor, and the condition of dual-screw pelletizer is specially：Temperature is 170 DEG C -185 DEG C, and screw speed is 130rpm-
180rpm, screw slenderness ratio L/D are 30-50.
Illustrated with reference to specific embodiment：
Embodiment one
The present invention provides a kind of Wholly-degradable material, and the Wholly-degradable material uses double membrane structure, including the first tunic and the
Two tunics；Wherein, the raw material components of the first tunic by weight, including the weight portion of titanium dioxide 0.05, the weight of magnesium stearate 0.2
Amount part, the weight portion of phenyl salicylate 0.1, the weight portion of DBPC 2,6 ditertiary butyl p cresol 0.05, the weight of low density polyethylene (LDPE) 2436H 5
Part and the weight portion of LLDPE 7,042 94.6；The raw material components of the second tunic by weight, including：Corn
The weight portion of starch 15, the weight portion of nano silicon 1, the weight portion of 3- aminopropyl triethoxysilanes 2, polyvinyl alcohol 1,799 10
Weight portion, the weight portion of titanium dioxide 0.05, the weight portions of low density polyethylene (LDPE) 2436H 3 and LLDPE 7042
68.95 weight portions.
By above-mentioned raw materials component, the preparation method of the Wholly-degradable material provided using the present invention prepares Wholly-degradable material：
S101：The ball-milling treatment under conditions of rotating speed is 350rpm is carried out after each raw material components of the first tunic are mixed
300min, is granulated in dual-screw pelletizer afterwards, obtains ground floor membrane degradation plastic grain；The bar of dual-screw pelletizer
Part is：Temperature is 183 DEG C, and screw speed is 150rpm, and screw slenderness ratio L/D is 35.
S102：Granulated after each raw material components in second tunic are well mixed, obtain second layer membrane degradation plastic grain；
Wherein, by the mixture and water of starch, 3- aminopropyl triethoxysilanes, titanium dioxide and polyvinyl alcohol 1799 according to 1：3
Mass ratio mixes, and is then 50 DEG C in temperature, and it is 6.0 that rotating speed adjusts pH value to stir 50min under conditions of 150rpm, afterwards；
It is subsequently adding nano silicon to continue to stir, regulation pH value is 3.8；Product that pH value is 3.8 is dried, afterwards and low-density
Polyethylene and LLDPE mixing after rotating speed be 350rpm under conditions of ball-milling treatment 300min, afterwards in double spiral shells
Granulated in bar comminutor, obtained second layer membrane degradation plastic grain；The condition of dual-screw pelletizer is：Temperature is 183 DEG C,
Screw speed is 150rpm, and screw slenderness ratio L/D is 35.
S103：Ground floor membrane degradation plastic grain and second layer membrane degradation plastic grain are entered in double-layer coextrusion inflation film manufacturing machine
Row coextrusion blow, and be 3 μm by the thickness that the product after blowing is adjusted to the first tunic, the thickness of the second tunic is 6 μm, is obtained
Degradable mulch film needed for the present invention.The condition of double-layer coextrusion inflation film manufacturing machine is：Temperature is 155 DEG C, and blow-up ratio is 3.3, traction speed
It is 8m/min to spend.
Embodiment two
The present invention provides a kind of Wholly-degradable material, and the Wholly-degradable material uses double membrane structure, including the first tunic and the
Two tunics；Wherein, the raw material components of the first tunic by weight, including the weight portion of ferric stearate 0.03, di-iron trioxide
0.01 weight portion, the weight portion of barium stearate 0.2,4,4 '-isopropylidene double (phenol salicylate) 0.1 weight portion, salicylic acids pair
The weight portion of tert-butyl group phenyl ester 0.1, the weight portion of 2,4,6- tri-butyl-phenols 0.05, the weight portions of low density polyethylene (LDPE) 2426H 5, line
The weight portions of property low density polyethylene (LDPE) 0218D 10 and the weight portions of 7042N 84.51；The raw material components of the second tunic are by weight
Meter, including：It is the weight portion of farina 20, the weight portion of nano silicon 3, the weight portion of 3- aminopropyl trimethoxysilanes 3, poly-
The weight portion of vinyl alcohol 1,788 14, the weight portion of ferric stearate 0.05, the weight portions of low density polyethylene (LDPE) 2426H 3, linea low density gather
The weight portions of ethene 0218D 5 and the weight portions of 7042N 51.95.
By above-mentioned raw materials component, the preparation method of the Wholly-degradable material provided using the present invention prepares Wholly-degradable material：
S101：The ball-milling treatment under conditions of rotating speed is 500rpm is carried out after each raw material components of the first tunic are mixed
200min, is granulated in dual-screw pelletizer afterwards, obtains ground floor membrane degradation plastic grain；The bar of dual-screw pelletizer
Part is：Temperature is 170 DEG C, and screw speed is 180rpm, and screw slenderness ratio L/D is 45.
S102：Granulated after each raw material components in second tunic are well mixed, obtain second layer membrane degradation plastic grain；
Wherein, by the mixture and water of starch, 3- aminopropyl trimethoxysilanes, ferric stearate and polyvinyl alcohol 1788 according to 1：5
Mass ratio mixes, and is then 40 DEG C in temperature, and it is 5.8 that rotating speed adjusts pH value to stir 30min under conditions of 250rpm, afterwards；
It is subsequently adding nano silicon to continue to stir, regulation pH value is 3.5；Product that pH value is 3.5 is dried, afterwards and low-density
Polyethylene and LLDPE mixing after rotating speed be 500rpm under conditions of ball-milling treatment 200min, afterwards in double spiral shells
Granulated in bar comminutor, obtained second layer membrane degradation plastic grain；The condition of dual-screw pelletizer is：Temperature is 170 DEG C,
Screw speed is 180rpm, and screw slenderness ratio L/D is 45.
S103：Ground floor membrane degradation plastic grain and second layer membrane degradation plastic grain are entered in double-layer coextrusion inflation film manufacturing machine
Row coextrusion blow, and be 2 μm by the thickness that the product after blowing is adjusted to the first tunic, the thickness of the second tunic is 5 μm, is obtained
Degradable mulch film needed for the present invention.The condition of double-layer coextrusion inflation film manufacturing machine is：Temperature is 160 DEG C, and blow-up ratio is 3.1, traction speed
It is 10m/min to spend.
Embodiment three
The present invention provides a kind of Wholly-degradable material, and the Wholly-degradable material uses double membrane structure, including the first tunic and the
Two tunics；Wherein, the raw material components of the first tunic by weight, including the weight portion of cobaltous octadecanate 0.01, the weight of manganese oxide 0.01
Amount part, the weight portion of calcium stearate 0.1, the weight portion of barium laurate 0.1, the weight portion of resorcinol monobenzoate 0.02,4- hydroxyl first
Base -2, the weight portion of 6- DI-tert-butylphenol compounds 0.03, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters
0.03 weight portion, the weight portions of low density polyethylene (LDPE) LD662 5 and the weight portions of LLDPE 218W 94.62；Second
The raw material components of tunic by weight, including：The weight portion of tapioca 25, the weight portion of nano silicon 4,3- glycidols
The weight portion of ether oxygen propyl trimethoxy silicane 4, the weight portion of polyvinyl alcohol 1,788 17, the weight portion of cobaltous octadecanate 0.02, manganese dioxide
0.02 weight portion, the weight portions of low density polyethylene (LDPE) LD662 4 and the weight portions of LLDPE 218W 45.96.
By above-mentioned raw materials component, the preparation method of the Wholly-degradable material provided using the present invention prepares Wholly-degradable material：
S101：The ball-milling treatment under conditions of rotating speed is 400rpm is carried out after each raw material components of the first tunic are mixed
250min, is granulated in dual-screw pelletizer afterwards, obtains ground floor membrane degradation plastic grain；The bar of dual-screw pelletizer
Part is：Temperature is 175 DEG C, and screw speed is 130rpm, and screw slenderness ratio L/D is 50.
S102：Granulated after each raw material components in second tunic are well mixed, obtain second layer membrane degradation plastic grain；
Wherein, by starch, 3- glycidyl ether oxygen propyl trimethoxy silicanes, cobaltous octadecanate, manganese dioxide and polyvinyl alcohol 1788
Mixture is with water according to 1：4 mass ratio mixing, then temperature be 45 DEG C, rotating speed be 180rpm under conditions of stir 40min,
Regulation pH value is 6.3 afterwards；It is subsequently adding nano silicon to continue to stir, regulation pH value is 3.5；By the product that pH value is 3.5
Thing is dried, after mixing with low density polyethylene (LDPE) and LLDPE afterwards under conditions of rotating speed is 400rpm at ball milling
Reason 250min, is granulated in dual-screw pelletizer afterwards, obtains second layer membrane degradation plastic grain；Dual-screw pelletizer
Condition is：Temperature is 175 DEG C, and screw speed is 130rpm, and screw slenderness ratio L/D is 50.
S103：Ground floor membrane degradation plastic grain and second layer membrane degradation plastic grain are entered in double-layer coextrusion inflation film manufacturing machine
Row coextrusion blow, and be 2 μm by the thickness that the product after blowing is adjusted to the first tunic, the thickness of the second tunic is 6 μm, is obtained
Degradable mulch film needed for the present invention.The condition of double-layer coextrusion inflation film manufacturing machine is：Temperature is 158 DEG C, and blow-up ratio is 3.2, traction speed
It is 9m/min to spend.
Example IV
The present invention provides a kind of Wholly-degradable material, and the Wholly-degradable material uses double membrane structure, including the first tunic and the
Two tunics；Wherein, the raw material components of the first tunic by weight, including the weight of ferric dimethyl dithiocarbamate 0.06
Part, the weight portion of Magnesium dilaurate 0.4, the weight portion of ESCALOL 567 0.3,2,2 '-di-2-ethylhexylphosphine oxide (4- ethyls -6-
Tert-butyl phenol) 0.15 weight portion, low density polyethylene (LDPE) LD6008 weight portions and LLDPE 9,020 91.09
Weight portion；The raw material components of the second tunic by weight, including：The weight portion of cornstarch 45, the weight of nano silicon 5
Part, the weight portion of 3- methacryloxypropyl trimethoxy silanes 5, the weight portion of polyvinyl alcohol 0,588 30, DMDS generation
The weight portion of carbamic acid iron 0.06, the weight portions of low density polyethylene (LDPE) LD600 5 and the weight of LLDPE 90209.5
Part.
By above-mentioned raw materials component, the preparation method of the Wholly-degradable material provided using the present invention prepares Wholly-degradable material：
S101：The ball-milling treatment under conditions of rotating speed is 350rpm is carried out after each raw material components of the first tunic are mixed
300min, is granulated in dual-screw pelletizer afterwards, obtains ground floor membrane degradation plastic grain；The bar of dual-screw pelletizer
Part is：Temperature is 183 DEG C, and screw speed is 150rpm, and screw slenderness ratio L/D is 35.
S102：Granulated after each raw material components in second tunic are well mixed, obtain second layer membrane degradation plastic grain；
Wherein, by starch, 3- methacryloxypropyl trimethoxy silanes, ferric dimethyl dithiocarbamate and polyvinyl alcohol
0588 mixture is with water according to 1：3 mass ratio mixing, is then 50 DEG C in temperature, and rotating speed is stirring under conditions of 150rpm
50min, it is 6.0 that pH value is adjusted afterwards；It is subsequently adding nano silicon to continue to stir, regulation pH value is 3.8；It is by pH value
3.8 product is dried, in the condition that rotating speed is 350rpm after mixing with low density polyethylene (LDPE) and LLDPE afterwards
Lower ball-milling treatment 300min, is granulated in dual-screw pelletizer afterwards, obtains second layer membrane degradation plastic grain；Twin-screw
The condition of comminutor is：Temperature is 183 DEG C, and screw speed is 150rpm, and screw slenderness ratio L/D is 35.
S103：Ground floor membrane degradation plastic grain and second layer membrane degradation plastic grain are entered in double-layer coextrusion inflation film manufacturing machine
Row coextrusion blow, and be 2 μm by the thickness that the product after blowing is adjusted to the first tunic, the thickness of the second tunic is 6 μm, is obtained
Degradable mulch film needed for the present invention.The condition of double-layer coextrusion inflation film manufacturing machine is：Temperature is 155 DEG C, and blow-up ratio is 3.3, traction speed
It is 8m/min to spend.
Embodiment five
The present invention provides a kind of Wholly-degradable material, and the Wholly-degradable material uses double membrane structure, including the first tunic and the
Two tunics；Wherein, the raw material components of the first tunic by weight, including the weight portion of diethyldithiocar bamic acid cerium 1, the moon
The weight portion of cinnamic acid calcium 0.3, the weight portion of UV-531 0.25, four [β-(3,5- di-t-butyl -4- hydroxyls
Phenyl) propionic acid] weight portion of pentaerythritol ester 0.2, the weight portions of low density polyethylene (LDPE) 20,12T,N26 10 and linear low density polyethylene
The weight portion of alkene 9,042 88.25；The raw material components of the second tunic by weight, including：The weight portion of farina 30, nanometer
The weight portion of silica 3, the weight portion of 3- aminopropyl triethoxysilanes 3, the weight portion of polyvinyl alcohol 0,578 20, the sulphur of diethyl two
For the weight portion of carbamic acid cerium 1, the weight portions of low density polyethylene (LDPE) 20,12T,N26 4 and the weight of LLDPE 9,020 39
Amount part.
By above-mentioned raw materials component, the preparation method of the Wholly-degradable material provided using the present invention prepares Wholly-degradable material：
S101：The ball-milling treatment under conditions of rotating speed is 500rpm is carried out after each raw material components of the first tunic are mixed
200min, is granulated in dual-screw pelletizer afterwards, obtains ground floor membrane degradation plastic grain；The bar of dual-screw pelletizer
Part is：Temperature is 170 DEG C, and screw speed is 180rpm, and screw slenderness ratio L/D is 45.
S102：Granulated after each raw material components in second tunic are well mixed, obtain second layer membrane degradation plastic grain；
Wherein, by the mixture of starch, 3- aminopropyl triethoxysilanes, diethyldithiocar bamic acid cerium and polyvinyl alcohol 0578
With water according to 1：5 mass ratio mixing, is then 40 DEG C in temperature, and rotating speed is adjusted afterwards to stir 30min under conditions of 250rpm
Section pH value is 5.8；It is subsequently adding nano silicon to continue to stir, regulation pH value is 3.5；The product that pH value is 3.5 is dried,
After mixing with low density polyethylene (LDPE) and LLDPE afterwards rotating speed be 500rpm under conditions of ball-milling treatment
200min, is granulated in dual-screw pelletizer afterwards, obtains second layer membrane degradation plastic grain；The bar of dual-screw pelletizer
Part is：Temperature is 170 DEG C, and screw speed is 180rpm, and screw slenderness ratio L/D is 45.
S103：Ground floor membrane degradation plastic grain and second layer membrane degradation plastic grain are entered in double-layer coextrusion inflation film manufacturing machine
Row coextrusion blow, and be 2 μm by the thickness that the product after blowing is adjusted to the first tunic, the thickness of the second tunic is 6 μm, is obtained
Degradable mulch film needed for the present invention.The condition of double-layer coextrusion inflation film manufacturing machine is：Temperature is 160 DEG C, and blow-up ratio is 3.1, traction speed
It is 10m/min to spend.
Embodiment six
The present invention provides a kind of Wholly-degradable material, and the Wholly-degradable material uses double membrane structure, including the first tunic and the
Two tunics；Wherein, the raw material components of the first tunic by weight, including the weight portion of cerium stearate 0.5, the weight of calcium stearate 0.3
Amount part, the weight portion of resorcinol monobenzoate 0.2, the weight portion of 4 hydroxymethyl 2,6 di t butyl phenol 0.1, low-density are gathered
The weight portions of ethene 2426H 8 and the weight portions of LLDPE 7042T 90.9；The raw material components of the second tunic are by weight
Amount part meter, including：The weight portion of tapioca 35, the weight portion of nano silicon 4, the weight portion of 3- aminopropyl triethoxysilanes 4,
The weight portion of polyvinyl alcohol 0,578 23, the weight portion of cerium stearate 0.5, weight portions of low density polyethylene (LDPE) 2426H 4 and linear low close
The degree weight portion of polyethylene 9,020 29.5.
By above-mentioned raw materials component, the preparation method of the Wholly-degradable material provided using the present invention prepares Wholly-degradable material：
S101：The ball-milling treatment under conditions of rotating speed is 400rpm is carried out after each raw material components of the first tunic are mixed
250min, is granulated in dual-screw pelletizer afterwards, obtains ground floor membrane degradation plastic grain；The bar of dual-screw pelletizer
Part is：Temperature is 175 DEG C, and screw speed is 130rpm, and screw slenderness ratio L/D is 50.
S102：Granulated after each raw material components in second tunic are well mixed, obtain second layer membrane degradation plastic grain；
Wherein, by starch, 3- glycidyl ether oxygen propyl trimethoxy silicanes, cobaltous octadecanate, manganese dioxide and polyvinyl alcohol 1788
Mixture is with water according to 1：4 mass ratio mixing, then temperature be 45 DEG C, rotating speed be 180rpm under conditions of stir 40min,
Regulation pH value is 6.3 afterwards；It is subsequently adding nano silicon to continue to stir, regulation pH value is 3.5；By the product that pH value is 3.5
Thing is dried, after mixing with low density polyethylene (LDPE) and LLDPE afterwards under conditions of rotating speed is 400rpm at ball milling
Reason 250min, is granulated in dual-screw pelletizer afterwards, obtains second layer membrane degradation plastic grain；Dual-screw pelletizer
Condition is：Temperature is 175 DEG C, and screw speed is 130rpm, and screw slenderness ratio L/D is 50.
S103：Ground floor membrane degradation plastic grain and second layer membrane degradation plastic grain are entered in double-layer coextrusion inflation film manufacturing machine
Row coextrusion blow, and be 2 μm by the thickness that the product after blowing is adjusted to the first tunic, the thickness of the second tunic is 6 μm, is obtained
Degradable mulch film needed for the present invention.The condition of double-layer coextrusion inflation film manufacturing machine is：Temperature is 158 DEG C, and blow-up ratio is 3.2, traction speed
It is 9m/min to spend.
Embodiment seven
The present invention provides a kind of Wholly-degradable material, and the Wholly-degradable material uses double membrane structure, including the first tunic and the
Two tunics；Wherein, the raw material components of the first tunic by weight, including：The weight portion of Praseodymium Stearate 0.03, the weight of ferrocene 0.05
Amount part, the weight portion of zinc laurate 0.30, the weight portion of resorcinol monobenzoate 0.20, the weight of 2,4,6- tri-butyl-phenol 0.10
Amount part, the weight portions of low density polyethylene (LDPE) 20,12T,N26 8, the weight portion of LLDPE 1,799 46.5 and 0588
46.5 weight portions；The raw material components of the second tunic by weight, including：The weight portion of cornstarch 15, the weight of farina 15
It is amount part, the weight portion of nano silicon 5, the weight portion of 3- aminopropyl trimethoxysilanes 5, the weight portion of polyvinyl alcohol 1,799 20, hard
The weight portion of resin acid praseodymium 0.03, the weight portion of ferrocene 0.05, the weight portions of low density polyethylene (LDPE) 20,12T,N26 5, linear low density polyethylene
The weight portion of alkene 9,020 33 and the weight portions of FV149M 33.
By above-mentioned raw materials component, the preparation method of the Wholly-degradable material provided using the present invention prepares Wholly-degradable material：
S101：The ball-milling treatment under conditions of rotating speed is 400rpm is carried out after each raw material components of the first tunic are mixed
250min, is granulated in dual-screw pelletizer afterwards, obtains ground floor membrane degradation plastic grain；The bar of dual-screw pelletizer
Part is：Temperature is 175 DEG C, and screw speed is 130rpm, and screw slenderness ratio L/D is 50.
S102：Granulated after each raw material components in second tunic are well mixed, obtain second layer membrane degradation plastic grain；
Wherein, the mixture and water of starch, 3- aminopropyl trimethoxysilanes, Praseodymium Stearate, ferrocene and polyvinyl alcohol 1799 are pressed
According to 1：4 mass ratio mixing, is then 45 DEG C in temperature, and rotating speed adjusts pH value afterwards to stir 40min under conditions of 180rpm
It is 6.3；It is subsequently adding nano silicon to continue to stir, regulation pH value is 3.5；The product that pH value is 3.5 is dried, Zhi Houyu
Low density polyethylene (LDPE) and LLDPE mixing after rotating speed be 400rpm under conditions of ball-milling treatment 250min, afterwards
Granulated in dual-screw pelletizer, obtained second layer membrane degradation plastic grain；The condition of dual-screw pelletizer is：Temperature is
175 DEG C, screw speed is 130rpm, and screw slenderness ratio L/D is 50.
S103：Ground floor membrane degradation plastic grain and second layer membrane degradation plastic grain are entered in double-layer coextrusion inflation film manufacturing machine
Row coextrusion blow, and be 3 μm by the thickness that the product after blowing is adjusted to the first tunic, the thickness of the second tunic is 4 μm, is obtained
Degradable mulch film needed for the present invention.The condition of double-layer coextrusion inflation film manufacturing machine is：Temperature is 158 DEG C, and blow-up ratio is 3.2, traction speed
It is 9m/min to spend.
In order to further highlight the advantage of the preparation method of present invention offer, following contrast experiment is carried out；Hereinafter contrast real
Test using embodiment seven as benchmark, the unitary variant experiment of relevant parameter is carried out on this basis.
Comparative example one
In the comparative example in addition to pH value difference in step S102, remaining parameter is with embodiment seven.
Specifically, step S102 is：Granulated after each raw material components in second tunic are well mixed, obtain the second tunic
Degradative plastics particle；Wherein, by starch, 3- aminopropyl trimethoxysilanes, Praseodymium Stearate, ferrocene and polyvinyl alcohol 1799
Mixture is with water according to 1：4 mass ratio mixing, then temperature be 45 DEG C, rotating speed be 180rpm under conditions of stir 40min；
Nano silicon is added to continue to stir afterwards, regulation pH value is 3.5；Product that pH value is 3.5 is dried, afterwards and low-density
Polyethylene and LLDPE mixing after rotating speed be 400rpm under conditions of ball-milling treatment 250min, afterwards in double spiral shells
Granulated in bar comminutor, obtained second layer membrane degradation plastic grain；The condition of dual-screw pelletizer is：Temperature is 175 DEG C,
Screw speed is 130rpm, and screw slenderness ratio L/D is 50.
Comparative example two
In the comparative example in addition to pH value difference in step S102, remaining parameter is with embodiment seven.
Specifically, step S102 is：Granulated after each raw material components in second tunic are well mixed, obtain the second tunic
Degradative plastics particle；Wherein, by starch, 3- aminopropyl trimethoxysilanes, Praseodymium Stearate, ferrocene and polyvinyl alcohol 1799
Mixture is with water according to 1：4 mass ratio mixing, then temperature be 45 DEG C, rotating speed be 180rpm under conditions of stir 40min,
Regulation pH value is 6.5 afterwards；It is subsequently adding nano silicon to continue to stir, regulation pH value is 3.5；By the product that pH value is 3.5
Thing is dried, after mixing with low density polyethylene (LDPE) and LLDPE afterwards under conditions of rotating speed is 400rpm at ball milling
Reason 250min, is granulated in dual-screw pelletizer afterwards, obtains second layer membrane degradation plastic grain；Dual-screw pelletizer
Condition is：Temperature is 175 DEG C, and screw speed is 130rpm, and screw slenderness ratio L/D is 50.
Comparative example three
In the comparative example in addition to pH value difference in step S102, remaining parameter is with embodiment seven.
Specifically, step S102 is：Granulated after each raw material components in second tunic are well mixed, obtain the second tunic
Degradative plastics particle；Wherein, by starch, 3- aminopropyl trimethoxysilanes, Praseodymium Stearate, ferrocene and polyvinyl alcohol 1799
Mixture is with water according to 1：4 mass ratio mixing, then temperature be 45 DEG C, rotating speed be 180rpm under conditions of stir 40min,
Regulation pH value is 5.7 afterwards；It is subsequently adding nano silicon to continue to stir, regulation pH value is 3.5；By the product that pH value is 3.5
Thing is dried, after mixing with low density polyethylene (LDPE) and LLDPE afterwards under conditions of rotating speed is 400rpm at ball milling
Reason 250min, is granulated in dual-screw pelletizer afterwards, obtains second layer membrane degradation plastic grain；Dual-screw pelletizer
Condition is：Temperature is 175 DEG C, and screw speed is 130rpm, and screw slenderness ratio L/D is 50.
Comparative example four
In the comparative example in addition to the condition difference of double-layer coextrusion inflation film manufacturing machine in step S103, the same embodiment of remaining parameter
Seven.
S103：Ground floor membrane degradation plastic grain and second layer membrane degradation plastic grain are entered in double-layer coextrusion inflation film manufacturing machine
Row coextrusion blow, and be 3 μm by the thickness that the product after blowing is adjusted to the first tunic, the thickness of the second tunic is 4 μm, is obtained
Mulch film.The condition of double-layer coextrusion inflation film manufacturing machine is：Temperature is 162 DEG C, and blow-up ratio is 2.9, and hauling speed is 11m/min.
In addition, the full-biodegradable film that various embodiments of the present invention and comparative example are obtained, system evaluation its performance：
First, mechanics performance determining
Specifically, the mechanical property of each embodiment and comparative example mulch film, specific number are tested according to GB/T 1040.3-2006
According to as shown in table 1.
The mechanical property of each embodiment of table 1 and comparative example mulch film
2nd, Chinese cabbage growth situation and Plastic-film disintegration are determined
Specifically, it is test plant from Chinese cabbage.According to the suitable Experimental Base of Chinese Cabbage environmental selection, selection
15m2Field as experiment sample prescription, altogether choose 12 experiment sample prescriptions, each sample prescription sow 100.The 1-7 layings of experiment sample prescription are real
The mulch film in example one to embodiment seven is applied, the mulch film in experiment sample prescription 8-11 laying comparative example one to comparative examples four tests sample prescription
The 12 commercially available degradative plastic films of laying, as a control group.Specifically, 3d is shelved after September is applied fertilizer to each sample sample prescription on the 15th, is then chosen
Full Chinese cabbage seeds are selected to be sowed.After two weeks, the emergence rate and plant height of Chinese cabbage, the concrete outcome such as institute of table 2 are checked
Show.Additionally, the observation cycle is carried out through the budding period and maturity period of Chinese cabbage since Chinese cabbage sows covering with plastic film to mulch film
By a definite date 90 world observation monitoring, physical record respectively investigate mulch film in cell start degraded time (i.e. mulch film occur first not
The time in the hole of regular triangular shape, the length of the longest edge in hole is more than 10cm or so), it is used when Plastic-film disintegration rate is more than 99%
Time, and during record 6 months residual film average value, it is specific as shown in table 3.
The influence of each embodiment of table 2 and comparative example mulch film to Chinese cabbage growth situation
The degraded situation of each embodiment of table 3 and comparative example mulch film
3rd, water resistance is determined
Specifically, according to each embodiment of GB1027-70 standard testings and the water absorption rate performance of comparative example mulch film.For each reality
The mulch film of example and comparative example is applied, 10cm × 10cm sizes are taken respectively, in being dried at 105 DEG C to constant weight (W0), it is subsequently placed in room temperature
Under the distilled water of (25 DEG C or so) collect, periodically take out, blot surface moisture with filter paper, weigh (Wi), calculate water absorption rate.Each
Embodiment is parallel to carry out 3 groups of experiments, then averages；Specific data are as shown in table 4.Water absorption rate (%)=[(Wi-W0)/W0]
×100。
The water absorption rate situation of each embodiment mulch film of table 4
| Embodiment | One | Two | Three | Four | Five | Six | Seven |
| Water absorption rate/% | 4.5 | 4.3 | 4.2 | 4.8 | 4.5 | 4.6 | 3.5 |
Certainly, except the situation that embodiment one is enumerated to embodiment seven, the species and weight proportion of other raw material components, system
Condition and parameter during standby etc. are also possible.
The Dryland biodegradable material that the present invention is provided, fully combines the advantage of polythene material and starch, its
Using double-decker, not only with excellent mechanical performance and water resistance, and it is easy to degraded, it is in actually used process
In, each several part can simultaneously reach degraded terminal, so as to eliminate conventional commercial degradative plastic film each several part drop in application process
The defect that solution speed differs.Additionally, the mulch film that the present invention is provided can simultaneously reach degraded terminal in actual use, from
And winding of the residual film to machinery is greatly reduced, and reduce influence of the residual film to next season crop and save human cost, enter
And significantly promote the development of agricultural productive force.
It is to be appreciated that term " first ", " second " are only used for describing purpose, and it is not intended that indicating or implying phase
To importance or the implicit quantity for indicating indicated technical characteristic.Thus, " first " is defined, the feature of " second " can be with
Express or implicitly include one or more this feature.In the description of the invention, " multiple " be meant that two with
On, unless otherwise expressly limited specifically.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means to combine specific features, structure, material or spy that the embodiment or example are described
Point is contained at least one embodiment of the invention or example.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.And, the specific features of description, structure, material or feature can be with office
Combined in an appropriate manner in one or more embodiments or example.Additionally, in the case of not conflicting, the skill of this area
Art personnel can be tied the feature of the different embodiments or example described in this specification and different embodiments or example
Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changes, replacing and modification.
Claims (10)
1. a kind of Wholly-degradable material, it is characterised in that the Wholly-degradable material uses double membrane structure, including the first tunic and
Two tunics, and first tunic degradation time more than second tunic degradation time；
Wherein, the raw material components of first tunic by weight, including：Degradation agent 0.01-0.10 weight portions, heat stabilizer
0.20-0.40 weight portions, light stabilizer 0.10-0.30 weight portions, antioxidant 0.05-0.20 weight portions, low density polyethylene (LDPE) 5-
10 weight portions and LLDPE 89-94.64 weight portions；
The raw material components of second tunic by weight, including：Starch 15-45 weight portions, nano silicon 1-5 weight
Part, silane coupler 2-5 weight portions, polyvinyl alcohol 10-30 weight portions, degradation agent 0.01-0.10 weight portions, low density polyethylene (LDPE)
3-5 weight portions and LLDPE 9.9-68.99 weight portions.
2. Wholly-degradable material according to claim 1, it is characterised in that：
The degradation agent includes titanium dioxide, di-iron trioxide, manganese dioxide, ferrocene, ferric stearate, manganese stearate, tristearin
Sour cobalt, copper stearate, cerium stearate, Lanthanum Stearate, Praseodymium Stearate, ferric dimethyl dithiocarbamate and diethyl-dithio
One or more in carbamic acid cerium；
The heat stabilizer includes barium stearate, calcium stearate, zinc stearate, strontium stearate, magnesium stearate, barium laurate, the moon
One or more in cinnamic acid calcium, zinc laurate and Magnesium dilaurate；
The light stabilizer includes phenyl salicylate, 4,4- isopropylidenes double (phenol salicylate), salicylic acids to tert-butyl benzene
In ester, resorcinol monobenzoate, ESCALOL 567 and UV-531
One or more；
The antioxidant includes BHT, 2,4,6- tri-butyl-phenols, 4- methylol -2,6- di-t-butyls
Phenol, butylhydroxy anisole, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and 2,2 '-sub-
One or more in methyl double (4- ethyl -6- tert-butyl phenols)；
The starch includes cornstarch, farina, potato starch, rice starch, pea starch, sorghum starch and cassava
One or more in starch；
The silane coupler includes 3- aminopropyl triethoxysilanes, 3- aminopropyl trimethoxysilanes, 3- glycidol ethers
One or more in oxygen propyl trimethoxy silicane, 3- methacryloxypropyl trimethoxy silanes.
3. Wholly-degradable material according to claim 1, it is characterised in that：
The melt index of the low density polyethylene (LDPE) is 0.5-5.0g/10min, the melt index of the LLDPE
It is 1.5-2.5g/10min；The degree of polymerization of the polyvinyl alcohol is 500-1800, and alcoholysis degree is 78%-99%.
4. Wholly-degradable material according to claim 3, it is characterised in that：
The low density polyethylene (LDPE) is from one or more in LD662,2012TN26,2426H, 2436H and LD600；
The LLDPE is from 7042,7042T, 9020,7042N, 7042K, 218W, 0218D, 9042 and
One or more in FV149M；
The polyvinyl alcohol is from one or more in 1799,1788,1778,0588 and 0578.
5. the Wholly-degradable material according to claim any one of 1-4, it is characterised in that：
The thickness of first tunic is 2-4 μm, and the thickness of second tunic is 4-8 μm.
6. Wholly-degradable material according to claim 5, it is characterised in that：
The raw material components of first tunic by weight, including：The weight portion of Praseodymium Stearate 0.03, the weight of ferrocene 0.05
Part, the weight portion of zinc laurate 0.30, the weight portion of resorcinol monobenzoate 0.20, the weight of 2,4,6- tri-butyl-phenol 0.10
Part, the weight portion of low density polyethylene (LDPE) 8 and the weight portion of LLDPE 93；
The raw material components of second tunic by weight, including：The weight portion of cornstarch 15, the weight of farina 15
Part, nano silicon 1-5 weight portions, the weight portion of 3- aminopropyl trimethoxysilanes 5, the weight portion of polyvinyl alcohol 20, stearic acid
The weight portion of praseodymium 0.03, the weight portion of ferrocene 0.05, the weight portion of low density polyethylene (LDPE) 5 and the weight of LLDPE 66
Part；
Wherein, the thickness of first tunic is 3 μm, and the thickness of the second tunic is 4 μm；The degree of polymerization of the polyvinyl alcohol is
1700, alcoholysis degree is 99%, and the low density polyethylene (LDPE) selects the weight such as 2012TN26, the LLDPE selection
The 9020 and FV149M of part.
7. the preparation method of the Wholly-degradable material described in any one of claim 1-6, it is characterised in that comprise the following steps：
S101：Ball-milling treatment is carried out after each raw material components of the first tunic are mixed, is granulated afterwards, obtain the modeling of ground floor membrane degradation
Material particle；
S102：Granulated after each raw material components in second tunic are well mixed, obtain second layer membrane degradation plastic grain；Its
In, by the mixture and water of starch, silane coupler, degradation agent and polyvinyl alcohol according to 1：The mass ratio of (3-5) mixes and stirs
Mix uniform, regulation pH value is 5.8-6.3；It is subsequently adding nano silicon to continue to stir, regulation pH value is 3.5-4.0；By institute
State the product that pH value is 3.5-4.0 to dry, ball milling is carried out after mixing with low density polyethylene (LDPE) and LLDPE afterwards
Treatment, then granulates the product after the ball-milling treatment；
S103：The ground floor membrane degradation plastic grain and the second layer membrane degradation plastic grain are carried out into coextrusion blow.
8. the preparation method of the Wholly-degradable material described in claim 7, it is characterised in that：
In the S101 and the S102, the condition of the ball-milling treatment is：Rotating speed is 350-500rpm, and the time is
200min-300min；
In the S101 and the S102, the granulation is carried out in dual-screw pelletizer, and the dual-screw pelletizer
Condition is specially：Temperature is 170 DEG C -185 DEG C, and screw speed is 130rpm-180rpm, and screw slenderness ratio L/D is 30-50.
9. the preparation method of the Wholly-degradable material described in claim 7, it is characterised in that：
In the S102, the condition of stirring is specially：Temperature is 40 DEG C -50 DEG C, and rotating speed is 150rpm-250rpm, and the time is
30min-50min；
In the S103, coextrusion blow is carried out in double-layer coextrusion inflation film manufacturing machine, and the condition of double-layer coextrusion inflation film manufacturing machine is specially：Temperature
It is 155 DEG C -160 DEG C to spend, and blow-up ratio is 3.1-3.3, and hauling speed is 8m/min-10m/min.
10. the Wholly-degradable material described in any one of claim 1-6 is preparing mulch film, hyaline membrane and packaging material product or product
Application in additive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710166070.8A CN106883501A (en) | 2017-03-20 | 2017-03-20 | A kind of enhanced ecological degradative plastic film in Techniques in Dry-farming Areas and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710166070.8A CN106883501A (en) | 2017-03-20 | 2017-03-20 | A kind of enhanced ecological degradative plastic film in Techniques in Dry-farming Areas and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106883501A true CN106883501A (en) | 2017-06-23 |
Family
ID=59182019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710166070.8A Pending CN106883501A (en) | 2017-03-20 | 2017-03-20 | A kind of enhanced ecological degradative plastic film in Techniques in Dry-farming Areas and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106883501A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107312638A (en) * | 2017-06-29 | 2017-11-03 | 马辉 | Inhale color laundry sheet and preparation method and application |
| CN108276645A (en) * | 2018-02-05 | 2018-07-13 | 无锡市方成彩印包装有限公司 | A kind of Green Polymer packaging film and preparation method thereof that can cause the degradation of the multiple environment factor |
| CN108997648A (en) * | 2018-08-30 | 2018-12-14 | 北京国瑞新源投资有限公司 | A kind of compost type degradation refuse bag thin-film material and preparation method thereof |
| CN109181090A (en) * | 2018-09-26 | 2019-01-11 | 袁志平 | Dedicated Degradable environment protection mulch of milpa and preparation method thereof |
| CN109233079A (en) * | 2018-08-30 | 2019-01-18 | 宁夏中原塑业科技有限公司 | A kind of infiltration type degradative plastic film and preparation method thereof |
| CN111303907A (en) * | 2020-04-13 | 2020-06-19 | 曲阜师范大学 | Preparation method of dustproof sand-fixation environment-friendly liquid mulching material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0679172A1 (en) * | 1993-01-08 | 1995-11-02 | Novon International, Inc. | Biodegradable thermoplastic polymer blend compositions with accelerated biodegradation |
| WO2006135498A1 (en) * | 2005-06-09 | 2006-12-21 | Pliant Corporation | Controlled multilayer degradable film |
| CN104945682A (en) * | 2015-06-26 | 2015-09-30 | 苏州云舒新材料科技有限公司 | Thermoplastic starch based mulching film composite material and method for preparing the same |
| CN105028068A (en) * | 2015-07-27 | 2015-11-11 | 陆海荣 | Double-color and double-formula degradable mulching film and preparation method thereof |
| CN105037910A (en) * | 2015-07-27 | 2015-11-11 | 陆海荣 | Double-formula degradable mulching film for planting with double ridges and furrows and preparation method of double-formula degradable mulching film |
| CN105075751A (en) * | 2015-07-27 | 2015-11-25 | 陆海荣 | Double-degradable environmental protecting mulching film and manufacturing method thereof |
-
2017
- 2017-03-20 CN CN201710166070.8A patent/CN106883501A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0679172A1 (en) * | 1993-01-08 | 1995-11-02 | Novon International, Inc. | Biodegradable thermoplastic polymer blend compositions with accelerated biodegradation |
| WO2006135498A1 (en) * | 2005-06-09 | 2006-12-21 | Pliant Corporation | Controlled multilayer degradable film |
| CN104945682A (en) * | 2015-06-26 | 2015-09-30 | 苏州云舒新材料科技有限公司 | Thermoplastic starch based mulching film composite material and method for preparing the same |
| CN105028068A (en) * | 2015-07-27 | 2015-11-11 | 陆海荣 | Double-color and double-formula degradable mulching film and preparation method thereof |
| CN105037910A (en) * | 2015-07-27 | 2015-11-11 | 陆海荣 | Double-formula degradable mulching film for planting with double ridges and furrows and preparation method of double-formula degradable mulching film |
| CN105075751A (en) * | 2015-07-27 | 2015-11-25 | 陆海荣 | Double-degradable environmental protecting mulching film and manufacturing method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 黄文润 编著: "《硅烷偶联剂及硅树脂》", 31 August 2010, 四川出版集团•四川科学技术出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107312638A (en) * | 2017-06-29 | 2017-11-03 | 马辉 | Inhale color laundry sheet and preparation method and application |
| CN108276645A (en) * | 2018-02-05 | 2018-07-13 | 无锡市方成彩印包装有限公司 | A kind of Green Polymer packaging film and preparation method thereof that can cause the degradation of the multiple environment factor |
| CN108997648A (en) * | 2018-08-30 | 2018-12-14 | 北京国瑞新源投资有限公司 | A kind of compost type degradation refuse bag thin-film material and preparation method thereof |
| CN109233079A (en) * | 2018-08-30 | 2019-01-18 | 宁夏中原塑业科技有限公司 | A kind of infiltration type degradative plastic film and preparation method thereof |
| CN109181090A (en) * | 2018-09-26 | 2019-01-11 | 袁志平 | Dedicated Degradable environment protection mulch of milpa and preparation method thereof |
| CN111303907A (en) * | 2020-04-13 | 2020-06-19 | 曲阜师范大学 | Preparation method of dustproof sand-fixation environment-friendly liquid mulching material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106883501A (en) | A kind of enhanced ecological degradative plastic film in Techniques in Dry-farming Areas and preparation method thereof | |
| CN104031302B (en) | A kind of controllable oxidization biodegradable plastic master batch and preparation method thereof | |
| CN102408587B (en) | Environmentally-friendly controllable degradation agricultural film and preparation method thereof | |
| CN106084681B (en) | A kind of Biodegradable polyester composition | |
| CN106633704A (en) | Full-biodegradation mulch film for rice planting and production method thereof | |
| CN102942770A (en) | Completely-biodegradable agricultural mulching film | |
| CN103980684B (en) | A kind of toughness reinforcing water resistant starch plastics and preparation method thereof | |
| CN106905597A (en) | A kind of compound Wholly-degradable material and preparation method thereof | |
| CN106566261A (en) | Crop waste degradable mulching film and preparing method thereof | |
| CN105504704B (en) | Monoethanolamine activates sodium-based montmorillonite/polymer composite biodegradable blown film resin and preparation method | |
| CN107018827A (en) | A kind of environment whole degrading film material and preparation method thereof | |
| CN104403174A (en) | Environment-friendly controllable degradable film filled with high calcium carbonate | |
| CN106479132B (en) | A kind of degradation of plastic film master batch and the preparation method and application thereof | |
| Hongsriphan et al. | Properties of agricultural films prepared from biodegradable poly (butylene succinate) adding natural sorbent and fertilizer | |
| EP2463328A2 (en) | Biodegradable polymer film with controlled degree of biodegradability comprising mixture of polyvinyl alcohol and cellulose polymer and preparation method thereof | |
| CN110437590A (en) | A kind of starch-base biodegradation food package film and preparation method thereof that composite nano materials are modified | |
| CN109161173A (en) | A kind of controllable starch-base biodegradation agricultural mulching | |
| CN102660068A (en) | Controllable sugarcane photo-thermal degradable mulch film | |
| CN103483661A (en) | Degradable mulching film and preparation method thereof | |
| Ghobashy et al. | Optimal the mechanical properties of bioplastic blend based algae-(lactic acid-starch) using gamma irradiation and their possibility to use as compostable and soil conditioner | |
| CN102295934B (en) | Liquid agricultural mulching film and production method thereof | |
| CN106589539A (en) | Biodegradable additive and plastic products with addition of additive | |
| CN102115549B (en) | Biodegradable starch-containing high polymer composition and preparation thereof | |
| CN101921421A (en) | Ecological-degradation plastic mulch | |
| CN112980167A (en) | Degradable agricultural mulching film and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170623 |